US3819700A - 2-(hydrocarbylthio)-2-(hydroxyimino)-acetamide s-oxides and derivatives - Google Patents

Abstract

2-(HYDROCARBYLTHIO - 2 - (HYDROXYIMINO)-ACETAMIDO S-OXIDES AND DERIVATIVES OF THE GENERAL FORMULA:

R2-N(-R3)-CO-C(=N-O-R4)-S(=O)N-R1

WHERE N IS 1 OR 2, R4 IS H,

-CO-R6, OR -CO-NH-R5

AND R1, R2, R3, R5, AND R6 ARE AS HEREINAFTER DEFINED, ARE USEFUL AS FUNGICIDES. THE COMPOUNDS ARE PREPARED BY OXIDATION OF THE CORRESPONDING SULFIDES.

Description

3,819,700 Z-(HYDROCARBYLTHIO) 2.- YDROXYIMINO)- ACETAMIDE S-OXIDES AND DERIVATIVES Russell F. Bellina, 763 Montclair Drive, Apt. 10, v ,ClaymonhDeL; 19703 I No Drawing. Continuation-in-part of abandonedapplicm tion 'Ser. No. 31,391, Apr. ,23, 1970. application Mar. 5, 1971, SenNd'. 121,573

Int. Cl. C07c' 103/12, 103/14, 103/22, 103/24 US. Cl. 260-561 S 12 Claims ABSTRACT OF THE 'msc osuau Z-(Hydrocarbylthio) 2 (hydroxyirnino)-acctamido S-oxides and derivativespf the generalformula:

., 'JRIH .OHZY w r useful as fungicides. The compounds are prepared by oxidation of the, corresponding sulfides I K 3 1(5317 drocarbylthio)" 2 (hydrocarbylcarbam 'loxyimihoF 51??? Pam 07 3,819,700 Patented June 25, 1974 SUMMARY OF Tiih NvEN rIo .This. invention comprises novel compounds OfLth a'c'etamides, andtheirus to destroy'pestssiich as insects,

ticks, mites, 'andfn'emato'des" Fungicidal acft ivit of; the

compounds "is not disclosed There" arecommercially available 'f i'riierousj cheinical compounds which "are fuiigicidal'ly act'ive, andwhich aid in preventing fungus-incited diseases in crops and orna- .1

mental plants. However all of these have practical de ficiencies which restrict their use. Among the deficiencies are excessive phytotoiricity to certain crops, high cost, discomfort to the applicator, toxicity hazard to the appli cator or the food-consumingpublic, inadequate or excescides with optimumcombination of effectiveness, safety, 7

compatibility, and-economy.

Of the organisms responsible for diseases on agricultural crops, the fungi classed as Phycomycetes are among the most virulent. The disorders caused by this group downy mildews of grapes and cu cur'bits, and Pythium root rots.

This invention providesf ungicidally active compounds which do exhibit a desirable-combination of eifectiveness,

safety, compatibility and-economy. Diseases caused by i through 12 carbon atoms substituted with 1 chlorine atom; alkenyl of 3 through 4 carbon atoms; cycloalkyl of 3 through 8 carbonatoms; cycloalkenyl of 5 through 8 carbon atoms; cycloalkylalkyl of Y6 through 7 carbon atoms; phenyl; benzyl;

o I CH2OR7, wherein R is alkyl of 1 through 6 carbon atoms;

' 0 /R2 R -o-N= :-b'-N R -S 0 P.

wherein 1 R R and R are as defined below, p is 1 or 2 and R is phenylene, xylylene or alkylene of 2 through 18 carbon atoms;

R and R are each separately selected from the group consisting of alkyl of 1 through 12 carbon atoms; alkenyl of 3 through 4 carbon atoms; cycloalkyl of 3 through 1w 10wcarbonatoms; cycloalkenyl of 5 through 8 carbon atoms; cycloalkylalkyl of 6 through 7 carbon atoms;

phenyl; or benzyl; with the provisos that (1) only one of R and-R can be phenyl or benzyl, and (2) the sum of carbon atoms in R and R can total no more than 12, except where both R and R are alkyl;

R and R taken together,-along with the nitrogen atom to which they are attached, are a ring containing one,

nitrogen atom and 3 through 6 carbon atoms; or are a morpbolino ring;

wherein/5 I I 7 l is alkyl of 1 through 8 carbon atoms; propargyl; alkenyl of 3 through 4 .carbon atoms; cycloalkyl of 3 through 8 carbonatoms; benzyl; phenyl; or phenyl substituted with 1 or 2 substituents selected from "halogen, nitro, methoxy, and methyl; R isalkyl of lthrou'gh 11 carbon atoms; alkyl of 1 through. 11 carbon atoms substituted with up-jo threes'ubstituents selected from chlorine, bror nine, fluorine, or with up to 2 substituents selected frorn alkoxy of 1 through 2 carbon atoms, or with one alkoxycarbonyl of 2 through 3rcarbon' atoms; cycloalkyl of 3 through 8 carbon atoms; alkenyl of 2 through 6 carbon atoms; cycloalkenyl of 4 through 8 carbon atoms; bicycloalkenyl of 7 through 10 carbon atoms; cycloalkenylalkyl of 5 through ll'carbon atoms; cycloalkylalkyl of 4 .throughll carbon atoms; bicycloalkyl of 7 through 9 carbon atoms; adamantyl; benzyl; alkoxy of 1 through 4 carbon atoms; alkoxy of 1 through 4 carbon atoms substituted with one bromine or chlorine, or with one alkoxy of 1 through 2 carbon responding sulfide carbon atoms; and n is l or 2.

- Preferred because .of higher activity 'are' those compounds of formulaIwherein: 1 n v I 4 R is alkyLofrl through 10 carbon atoms; or cycloalkyl of 5 through6 carbon atoms; R and R are"each 'separatelv'selected from the group consisting of alkyl of 1 through 6 carbon atoms"-and cycloalkyl of 5 through 6 carbon atoms; R and R taken together, along with the nitrogen atom to e, 9 h. i a aisysatbqn tqt 2 h Qu h 3 which they attached, are a ring containing one nitrogen and 4 through 6 carbon atoms; and R is hydrogen.

The invention also includes a method of making a compound of formula I which comprises oxidizing a corof the formulae? wherein: R R R and R are as defined above, except that when R is.. V p,

or an isocyanateof the formula R NCO.

with an acid halide of, the

This invention further encompasses a method of preventing injury due to fungi which comprises"applying,to the locus to be protected an effective amount of a corripound of formula I, and fungicidal compositions comprising a fungicidally elfective amount of a compound of formula I and a diluent and/or a surfactant.

DESCRIPTION OF THE INVENTIONrw.

' :The compounds of formula I are generallly 'pi' pared by oxidation of the corresponding sulfide offorrnula II.

Asn d atedeburtherr boyet egnutnbe t equivalents of oxidizing agent used per equivalent of compound of formula II is equal to sum" of n and p in the product of formula I. Compounds of formula II where R is 5- f lm- .1 ,ER" areor dinarily treated with four equivalents of the oxidizing agenfto'pro'duce the'fcorresponding disulfone, i.e a ch'r'np'oun'd of Formula Ilwhe're R is.

r R40N=C- N m T ES v.3 and n and"; are both 2. I

Thereaction is "conducted in an inert solvent such as chloroform'o'r' acetic acid at a temperature in the-range of -15 to +70 C. It is ideally run at -5 to 5 C., employing a very slow rate of addition (3 to 6 hours) of the oxidizing agent to the sulfide/solvent. The reaction is usually allowed to stir overnight after the addition of the oxidizing agent. The organic layer is then evaporated under reduced pressure to furnish a veryhigh yield of the sulfoxide or sulfone of formula I. The sulfoxides, sulfones and disulfones are usually highly crystalline.

If desired, the compounds of formula I wherein R "i v o .r can alternativey be prepared by first preparing the sulfoxide or sulfone of formula Iwherein R is H, then reacting the product'with anappropriate acid halide of the mu X7 Q"R r 4: where X is halogen, preferably chlorine, The reaction of the acid' chloride and: the" 2-(hydroxyiinino)-2-(hydrocarbylthib) -acetarnide s-oxide i's'car'ried'out in a solvent s i a acetonit'rile which v comm; one; equivalent "of a bas man as pyridine. The reaction 'is'belstidonducted are temperature of about OTC, but'may he'c arr'ied' out at any temperature'in therang'e dfabout '-"-l5 to +80 'Q,. When t ceman is cornplete (usually about 1 to 3 hours) the, solven removed iuhdertreduced pressure, then the product s, recrystallized from a solvent such s @Pwm l 'Wh n' the r qd s h Pu d b d o i w ll?" 9tt1a$rImt Y n id washing with water, drying, airdfiltering kizmoval of the solvent furnishestthe prodlict, hf ter analytically pure.

The preferred oxidizing agent is a 40% solution of perv acetic acid, although other conventional oxidizing agents such as m-chloroperbenzoic acid, 30% hydrogen peroxide, potassium permanganate, l-chlorotien z'otriazole, and nitric acid, can also be used. The oxidation reaction is illustrated by equation (A): i

I zl his reaction 'illustratedbgequation can alternatively be preparedby reacting an S-oxide of formula I wherein R is H with an isoeyanate of the formula R NCO in a solvent such as anhydrous acetonitrile which contains atcatalytic amount of a base such as triethylamine or triethylenediamine. The reaction is mildly exothermic. Temperatureis maintained-lathe ra'ng'eof to 50C; by cooling if necessary. =Reactio'n is generally complete in Ho 4 hoursfilhe product is"obtained ingood'yield by evaporation of thesolvents; These carbamates "of 2-(hydroxyimino) 2- (hydrocarbylthio) acetamide S-oxides' usually recrystalliz'e well fro'ni' isopropanolj.This reaction is illustrated by equation (C) i o=N?o mice- 4.

The sulfides oi? formulaIl: whereink are prepared by allowing cliketene to react with :an appropriate primary'or secondaryamine of the formula R R Nl-l; treating the product withznitrous; acid,- then chlorinating with chlorineo'I'he chlorination product is then allowed to react with a mercaptan followed by'treatment with by reaction sequence (D):

base such as sodium hydroxide; This process'is illustrated where R isthe same as R as defined above-except that a it cannot be and it can additionally be above, and where ,R? is the same.

wh n t i where X is halogen, preferably chlorine, or into the corresponding compound of formula II wherein R is by reaction with an isocyanate of, the formu1a-R NCO. The rzonditions for these reactions :are in general the same as those described for thereactionsillustrated by equations (B) and (C).

Preparation of the compounds of this invention is further illirstratedby the following examples; 1

' EXAMPLE 1' of "2-hydro1ryirnino Z-rnethylsulfonyl hLN prepara ion] ding t y a' e m de a .arA mixture 3 of 6. 0 .'parts of 2rhydroxyimino-2-methylthio-N N-dirnethylacetamide and, 120 parts 0f ,chloro- ,form is cooled to 5 to +5 and is treated dropwise I it with rl4.8..parts.of.40.%v.tperacetic acid vover a .75 minute periodThe reaction is then allowed to stir overnight at room temperature. The reaction mixture is concentrated toabout'Mr its original volume and the product filtered; Recrystallization of this 'product from isopropanol gives 5.1 a parts 'of Z-h'ydroxyimino-2-methylsulfonyl-N,N-di methylacetamide, m.p.-18l0180.5. v, l t

EXAMPLE'Z Preparation of 2 hydroxyirnino-2 cycloheirylsulfonyl- N,N-dimethylacetamide "Replacing'the starting'material of Example 1 with an equivalentamount of Z-hydroxyimino-2-cycl0hexy1- thio-N,N-dimethylacetamide, there is obtained 2-hydroxyimi'tio'-2-cyclohexylsulfonyl N,N dimethylacetamide, which isxrecrystallized from water/isopropanol, 2/ 1', m.p. 1885? EXAMPLE 3 Preparationbf 2-hydroxyimino-2-octylsulfonyl-N,N-

a diethylacetamide H Replacingthe starting material of Example 1 withl a'n equivalent amount of 2-hydroxyimino-2-octylthio-N,1I-

die'thylae'etaifiide; there is obtained 2-hydroxyimino-2 octylsulfonyl N,N-diethylamide, 1 which" is recrystallized from isopropanol/water, 3/2, mp. 125 12551.

" EXAMPLE 4 Prepara ioii'of 2-hydroxyimino-2-hexylsulfonyl N,N-diethylacetamide v Replacing; the starting materials of Example 1 with an equivalent amount of 2-hydroxyimino-2-hexylthi0-N,N 'dieth'ylacetamidej there is obtained 2-hydroxyi'mino-2- A hexylsulforiyl N,N-diethylacetamide.

f EXAMPLES a Preparation of Z-hydroxyimino-cyclohexylsulfonyl- 'lfl bl-(B-pentamethylene)acetarnide n Replacing the starting material of Example] with an "equivalent-amount of '2-hydroxyiminogcyclohexylthiosNt N-(3-pentai riethylene)acetarnide, there is obtained 2-hy-' droxyimino-eyclohexylsulfonyl-N,N-(3 l pentamethylene) acetamideQiVhicIi 'is recrystallized from benzene.

The product of step (d) canrthen be" onverted into v H the correspondingcornpound of formula IlI wherein R is w H EXAMPLEG H Preparation or 2-hydroxyimino-2-octy1sulfonyl- N,N-(S-tetramethylene)acetamide Replacing the starting material of Example l'with an equivalent amount of Z-hydroxyimino-Z-octylthio-N,N-(3- tetramethylene)acetamide, there is obtained Z-hydroxy- 75 imino-2-octylsulfonyl-N,N-(S-tetramethyIene)acetamide.

TABLE I-Continued Number a, v molesol v Amine Mercaptan oxidant Product v I Azirlrlirm Allylmereaptan I 2 2-tgxdiriixyimino-2-allylsulIonyl-N ,N-dirnethyleneaceti 6, Do... ..defiant. 3-chloropropylmercaptannne 7 2 2-hydr0xyimin0-2-(3-chl0ropropylsulfonyl)-N,N-dimethyleneacetamide. Cyclooetylamine Methyl mereaptan 2 Z-hyfigoxyimino-2-methylsultonyl-N-eyclooetylacet- .wa e. v.-": w, 2-cyelooctenylmnine do 2 2-hydgoxymino-Z-methylsulfonyl-N-(Z-eyclooetenyl) H aceam p z-butenylmnina do 2 Z-hygirgaxyimino-Z-methylsulfonyl-N-(2-butenyl)aeeta i 7; l t v a e.' 1 z' 2-eyclopentenylamiue Cyclohexyl mercaptan.-...; 2 2hydroxyimino-2-cyolohexylsulfony-N-(2-cyclopen-- I t r tenyDacetarnlde. a, N-methylcyclodeeylamiue Cyclooctyl mercaptam... J. 1 2-hydroxyimino-Z-cyelooctylsulfinyl-N-methyl-N- A cyclodecylacetanfide. M N-ethylbsnzylamlne, cyelopropylmercaptamflue 2 24% ydrog!ngl[gig-eye]opropylsulfonyl-N-ethyl-N- v I enzy cea e. 1 Cyclopentanemethylamlne... Cyclopeutanemethylmercaptan 2 2-hydroxyimino-2-(2-eyclopentauemethylsultouyh- 1 rim v I N-(cyclopentylmethyl)acetamide. e Dipropylamine 4-eycl00cteuylmercaptau..- 1 2-hydroxyimino-2-(4-cyclooctenylsulfinyI)-N;N- v A, J 7 'di ropylacetamide. Plperidlne Allyl mercaptan 2 2-hy rox o-2-allylsulfonyl-N,N-pentamethyleue- 7 -acetamide'.

EXAMPLE 10 a EXAMPLE 1s Preparation the methyl carbamate of 2-hydroxyirnino- 2-rnethylsulfonyl-N,N-dimethylacetamide v A solution of 14.0 parts of the methyl carbamate of 2-hydroxyimino-2-methylthio-N,N-dimethylacetamide and, 270 parts of chloroform is cooled to 5 to +5 and treated with 25.6 parts of 40% :peracetic acid over .a 75" minute period. The reaction isthen allowed to. stir'at room temperature overnight. The chloroform layer is separated, dried, and evaporated to furnish a white solidwhich is washed thoroughly with ether. Recrystallization of the product from isopropanol furnishes 13.0 parts of the methyl carbamate of Z-hydroxyimino-Z-methylsulfonyl=N,N-dimethylacetamide, mp. 178-179".

E AM E 11 Preparation-0f the methylcarbamate of 2-hydroxyimino-. 2- cyclohexylsulfonyl-N,N;dimethylacetamide Replacingthe starting'material of. Example 10 with, an equivalent amount ofthe methylcarbamate'of 2-hydroxyimino 4 2 cyclohexylthio-N,N-dimethylaeetamide, there'is obtained the methylcarbamate ojf2 hydroxyimino- 2-cyclohexylsulfonyl-N,N-dimethylacetamide, mp; 154.5- 155. l f

- Preparation'of the inethylcarbamate' of 2-hydroxyimino 2 methylsulfonyl-N,N-hexamethyleneacetamide I Replacing the starting material of Example 10"with an equivalent amount of the methylcar'bamatel'of Z-hydr'oxyiminO-Z-Sec-butylthio-N,N-dimethylacetamide, there is obtained the methylcarbamate of- 2-hydroxy-2-sec-butylsulfonyl-N,N-dimethylacetamide, m.p. 1145 115". 1i

, in EXAMPLE 14 Preparation of the methylcarbamate of 2-hydroxyimino q 2methylsulfonyl-N,N-diethylacetamidef j r "Replacing the starting material of Example 10 with equivalent amount of the methylcarba'mateof"2 hydroxym no-Z-me hylth orNfl-di hyla e d th re, s bb+ tained the methylcarbamate of Z-hYdroxyimirioQZ-friethyl" sulfonyl-N,N-diethylacetamide.

Preparation of p bromocarbanilate of Z-hydroxyimino; 2-methylsulfonyl-N,N-dimethylacetamide" Replacing the starting material of Example 10 with an equivalent amount of the p-bromocarbanilate of'2-hydroxyimino-Z-methylthio-N,N-dimcthylacetamide, there is obtained the p-bromocarbanilate of Z-hydroxyimino-L methylsulfonyl N,N dimethylacetamide, 'mp, 158.5 159. r

EXAMPLE 16 Preparation of the o-chlorocarbanilate of 2-hydroxyimino- 2-methylsulfonyl-N,N-dimethylacetamide Replacing the starting material of Example 10 with an equivalent amount of the o-chlorocarbanilate of 2-hydroxyimino-Z-methylthio-N,N-dimethylacetamide, there is obtained the o-chlorocarbanilate of 2-hyclroxyimino-2- methylsulfonyl-N,N-dimethylacetamide, m.p. 112-1135".

EXAMPLE 17 Preparation otythe hexylcarbamate of 2-hydroxyimin0-2- 4 2 methylsulfony1-N,N-dimethylacetamide Replacing the starting material of Example I0-with an eguivalent. .,amount of the hexylcarbamate pf 2hy droxyimino-Z-methylthio-N,N-dimethylacetamide, there is obtained the ,hiexylcarbamate of 2-hydroxyimino 2-methylg from ether, m.p. 81 81.5

A 1; Replacing the starting material of Example 10' with ansulfonyl-N,N-dimethylacetamide,

which is recrystallized EXAMPLE 18 Preparation of the methylcarbamate l-hydroxyimino- 2-methylsulfinyl-N,N-dimethylacetamide A so1utionof 50.0 parts of the methylcarbamate of 2- hydroxyimino Z-methylthio-N,N-dimethylacetamide and 750 parts of-chloroform is cooled to 5 to +5", and is treated with 40.0 parts of 40% peracetic acid overa 3 /2 hour periOdQThe reaction is then allowed to stir at room temperature overnight. The chloroform layer is sepa-' A from benzene/chloroform, 2/1'gives' 50.3 p'arts'of the'= I methylcarbamate 65,

rated, dried,- and evaporated giving an oil Which crystallines on standing. The solid is powderedand washed.

thoroughly with ether. Recrystallization of the product.

of 2-hydroxyimino-Z-methylsulfinyl- N,N dirnethylacetarnide, m.p. 7 Table II contains a listing, under'the column headed Product, of various compounds of formula I wherein iRiS t t 2 The are made by oxidizing the corresponding sulfide of formula II by the procedures illustrated by Ex- EXAMPLE To a solution of 5.2 parts of 2,2-(l,8-octamethylenecites downy'mildew of grape; Pseudope'i'onospora cubensis, which incites downy mildew of cucurbits; Venturia inaequalis, which incites apple scab; Uromyces phaseoli, which incites bean rust; Puccinia recondita, P. coroinata, and P. glumarum, which incite leaf rusts of wheat, oats,

dithio)bis(2-hydroxyimino p py a and grasses, respectively; Puccinia graminis tritici, which 1n parts of f a fi 9- added 3 n p incites stern rust of wheat and Piricularin oryzne which tion, 3.8 parts of 40% peracetic acid. The reaction is then i i bl of i allowed f0 I temperature 1S evapofated to The compounds of this invention provide protection ful' l' t (1 }y fi 10 from damage caused by certain fungi when applied to the dr xy -N p py proper locus by the methods described hereinafter and The Compounds llstedillnder the headmg Product In at a sufficient rate to exert the desired effect. They are ah e IV are examples of compounds of formula I Where especially suited for the protection of living plants such '0 as fruit-bearing trees, vegetable crops, horticultural crops (including ornamentals, small fruits, and berries), fiber crops, grain and seed crops, sugarcane, sugar beets, pineapple, forage and hay crops, beans, peas, soybeans, pea- R =H and R =R SO The compounds are prepared nuts, potatoes, sweet-potatoes, tobacco, hops, turf, and by the procedures illustrated in Example 25. The necessary pasture. disulfide intermediates of the formula Living plants may be protected from fungi by applying 0 one or more of the compounds of this invention to seeds, ll tuber s, bulbs, or other plant reproductive parts prior to planting, as well as to foliage, stems, and/or fruit of the I living plant. Living plants may also be protected by dipio ping the root system. Where R10 is Preferred rates of application for the compounds of R 0 this invention to foliage, stems, and/or fruit of living plants range from 0.25 to 70 kilos of active ingredient per hectare. More preferred rates are in the range of 0.5 to Rs S 3 kilosper hectare. The most preferred rates are in the are prepared by the reactions illustrated in reaction sef of P to 15 kllos P hectare- The optlmum an'lount quencc (D), Where 9 s The fi l products are within this range depends upon a number of variables prepared by oxidation of the disulfide intermediate with Whleh are Well known to those Skllled ill the aft of Plant four equivalents of the oxidant. protection. These variables include, but are not limited to,

TABLE IV Amine Dithiol Product Didodeeylamino 1,12-dodecane dithio1- 2,2-(1,1Z-dodecainethylenedisulionyl)bis(2-hydroxyimino-N,N-din-dodecylacetamide) Dil5opropy1amine. 1,18-octadecy1dithi0l 2,2-(1,18-0etadecamethylenedisulfonyl)bis(2-hydroxyimino-N,N-

diisopropylacetamide). N-methylpropylamine 1,4-benzene dithiol 2,2-(1,4-phenylenedisulfonyDbis(2-hydroxyimino-N-methyl-N- propylaeetamide). Piper-idine 1,6-hexane dithiol 2,2-(1,fi-hexamethylenedisulfonyl)bis(2-hydroxyimino-N,N-

pentamethyleneaeetannde). Morpholine 1,10-decane dithiolfl 2,2(1,10-decamethylenedisulfonyDbis(2-hydroxyimlno-N,N-3-

oxapentamethyleneacetamid Hexamethyleneimine- .ido --'2,2-(1,l0 decamethylenedisulfonyl)bis(2-hydroxyimino-N,N-

hexamethyleneacetamide). Diellylamine .-.-do 2,2-(1,10-decamethylenedisulfonyl)bis(2-hydroxyimino-N,N-

' diallylacetamide). Aniline -do 2,2'-(1,10decamethylenedisultonybbis(Z-hydroxyimino-N- phenylacetamide). Azindine -.d0 2,2-(1,IO-deeamethylenedisulionyl)bls(2-hydroxyimino-N,N- dimethyleneaeetamide N-ethylbenzylamine-. 1,7-heptane dithiol. 2,2-(1,7-heptamethylenedisulfonyl)bis(2-hydroxyimino-N-ethyl- N-benzylacetamide). 2-butenylamlne ..d0 2,2-(1,7-heptamethylenedisuhonyl)bis(2-hydroxyimino-N-(2- butenyDacetamide). Cyclohexanemethylamine ..d0 2,2-(l,7-heptamethylenedisullonyl)bis(2-hydroxyimino-N- (cyclohexymethyDacetamide). Cyeloheptylamine 1,3-propaue dithiol 2,2-(1,3-trimethylenedisulfonyl)bis(Z-hydroxyimino-Neyeloheptylacetamide). Diethylamine 1,4-butane dithiol 2,2-(1,i-tetramethylenedisulfonyl)bis(2-hydroxyimino-N,N-

- diethylacetamide). Dibutylamlne 1,9-nonane dithiol 2,2-(1,9-uonamethylenedisulfonyl) bis(2-hydroxyimino-N,N- dibutylacetamide). I

A wide variety of fungus-incited diseases of foliage, fruit, stems, and roots of growing plants are controlled by the compounds of this invention without damage to the host. Fruits, tuber, bulbs, roots, seeds, and other plant parts harvested for food, animal feeds, or for other purposes are protected from fungus deterioration during processing, distribution, and storage. Seeds, tuber, cuttings, and other plant propagation materials are protected from fungus attack during handling and storage,"as well as in the soil after planting.

The many fungi against which the compounds of this invention are effective may be represented by, but are not limited to, the following: Phytophthora infestans, which incites late blight of potato and tomato; Phytophthprq parasitica and P. citrophthora, which incite foot rot and brown fruit rot of citrus; Plasmopara viticola, which inthe disease to be controlled, weather conditions expected, the type of crop, stage of development of the 'crop, and the interval between applications. Applications within the range given may need to be repeated one or many more times at intervals of 1 to 60 days. Application to the foliage, stems, and fruit of living plants at the rates indicated above is generally accomplished by employing sprays, dusts, or aerosols containing the proper amount of active ingredient. For the control of fungi regularly present, applications often start prior to the time that the problem actually appears and continue on a predetermined schedule. I

Preferred rates for application to seeds, tubers, bulbs, or other plant reproductive parts range from 25 to 8,000 grams of active compound'of this invention per kilos of planting material treated. More preferred rates are in the range of 50 to 4,000 grams of active compound per 100 kilos. The most preferred rates are in the range of 100 to 2,000 grams per 100 kilos. Applications of this type are made from dusts, slurries, or solutions.

Preferred rates for dip applications to roots of living plants are in the range of 1 to 4,000 grams of active ingredient per 100 liters of water or other liquid carrier. More preferred rates are in the range of 2 to 2,000 grams per 100 liters. The most preferred rates are in the range of 4 to 1,000 grams per 100 liters.

Plant parts, such as fruits, tubers, bulbs, roots, and the like, harvested for food or feed are protected from decay and other deterioration caused by fungi during processing, distribution, and storage by treatment with an active compound of this invention. The plant parts to be so protected are dipped in a liquid bath containing the active ingredient, dusted with a finely divided preparation of the active ingredient, sprayed or misted with an aerosol. The liquid bath contains an amount of the active ingredient in the range of 1 to 5,000 parts per million of the vweight of the fluid. A more preferred range for the bath is 5 to 2,500 parts per million, and the most preferred range is to 1,000 parts per million. Dusts used for this type of application contain 0.01 to 10% by weight of the active ingredient. More preferred rates are in the range of 0.1 to 5%, and the most preferred rates are in the range of 0.2 to 2.5 percent by weight.

As indicated by the above discussion, the fungicidally active compounds will be applied in a variety of formulations including wettable powders, suspensions, emulsifiable concentrates, dusts, solutions, granules or pellets. These formulations will include one or more compounds of Formula I and can include surface-active agents, solid or liquid diluents and other materials as required to produce the desired formulation.

The surface-active agents act aswetting, dispersing and emulsifying agents which assist dispersion of the active material in the spray, and improve wetting of waxy foliage and the like by the spray. The surfactants can include such anionic, non-ionic and cationic agents as have been used heretofore in pesticidal compositions of similar type. A detailed list of such agents may be found in Detergents and Emulsifiers Annual, (John W. McCutcheon, Inc.). I

Anionic and non-ionic surfactants are preferred. Among the anionic surfactants, preferred ones are alkali and alkaline earth salts of alkylarylsulfonic acids, such as dodecylbenzenesulfonates and alkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodium lauryl sulfate, sodium N-methyl-N-oleoyltaurate, sodium dodecyldiphenyl ether disulfonate and the oleic acid ester of sodium 'isethionate. Among the non-ionic surfactants, preferred ones include alkenylphenyl polyethylene glycol ethers, polyoxyethylene derivatives of sorbitan fatty esters and longchainalcohols and mercaptans, as well as polyoxyethylene esters of fatty acids. l

Preferred dispersants are alkali and alkaline earth salts of lignosulfonic acids, salts of polymerized alkylarylsnlfonates which are sold under the Daxad and Darvanf trademarks, as well as methylcellulose, polyvinyl alcohol and the like. 7 V Surfactants are present in compositions of this invention in amounts up to about 20% by weight based on the total weight of the resulting composition. When larger amounts of surfactant are desired,as for improved wetting of, spreading over, or penetration into foliage, mixing in the spray tank is usually preferable forconvenience. Powder and dust preparations can be made by blending the active ingredient, with or without surfactant, with finely divided solids such as talcs, natural clays, pyrophyllite, diatomaceous earth; flours such as walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sodium silicoaluminate, sulfur and lime. In general, storage stability will be best when the system has a near neutral pH and has a lowlevel of moisture. The choice of diluents will then depend on the physical properties and shelf life desired. The compositions are made by thoroughly blending the active ingredient with the diluent and other additives. Usually a grinding step, as in a hammer mill or fluid energy mill, is included. The particles in dust and powder preparations are preferably less than microns in average diameter. With compounds which are highly water insoluble, improved activity may be obtained with still finer grinding.

Preferred wettable powder formulations will contain 40% or more active ingredient together with sufiicient surfactant and inert diluent to permit dispersion in water for spray application. Compositions intended for dust application will generally contain less than 50% active ingredient.

Powdered compositions can be converted to granules by adding a liquid, treating mechanically, and usually, drying. Mechanical devices such as granulating pans, mixers and extruders can be used. Compaction devices can be used without a liquid in the mixture. Water soluble binders, such as inorganic salts, urea, ligninsulfonates, methyl cellulose, and the like, can be included in these particulate formulations in amounts up to about 25% by Weight of the finished granule or pellet. Such materials also aid in disintegration of the pellet and release of the active ingredient under field conditions. Alternatively, a solution or suspension of the active ingredient can be sprayed on the surface of preformed granules of clay, vermiculite, corn cob and the like. Surfactants may also be included in formulations of the latter type.

Suspension formulations can be made in water, or in organic solvents, or in mixtures of water and Water-miscible organic solvents in which the active ingredient has a solubility under about 0.1%. The preparations usually include, in addition to the active ingredient and liquid carrier, surfactants, viscosity control agents, anti-microbial agents and other modifiers. They are prepared by grinding the components in a sand mill or pebble mill preferably until the average particle size is under 20 microns.

Hydrocarbon and other flammable carriers should have boiling points above about C. for safety in handling. Suspensions in hydrocarbons are suitable for extension in spray oils and, by inclusion of a suitable emulsifying agent, may also be made sprayable from water.

Organic liquids suitable for preparation of solutions, suspensions and emulsifiable concentrates of the compounds of this invention include alcohols, glycols, Cellosolves, Carbitols, ketones, esters, sulfamides, amides, paraflinic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons. Choice of a liquid is dictated by the solubility of the active compound to be used and whether a suspension or solution is desired. The class of compounds represented by Formula I is particularly variable in solubility characteristics, so it is not possible to generalize in'the use of particular solvents for particular purposes.

All compositions intended for spray use can contain minor amounts of additives to reduce foam, inhibit corrosion, prevent claying, reduce caking, etc. as the conditions of use may dictate. The conditions of need for and use of such additives are generally known in the art.

The compounds of this invention can often be used to advantage in combinations or mixtures with one or more of the fungicides, bactericides, insecticides, acari cides, or nematocides available on the market today. The

combinations or mixtures can be made by the applicator just prior to use (as in the tank of a sprayer) or included in a single composition by the manufacturer or a subsequent processor as will be discussed in more detail hereinafter. Illustrative of the materials that may be included in such combinations or mixtures are the following:

1,2,3,4, 10,l0-hexachloro 1,4,4a,5,8,8a-heXahydro-l,4-

endo-exo-S,8-dimethanonaphthalene (aldrin) 1,2,3,4,5,6-hexachlorocyclohexane (lindane);

2,3,4,5,6,7,8,8-ctachloro-4,7-methano-3a-4,7,7a-

tetrahydroindane;

1,2,3,4,10,l0-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-

octahydro-1,4-end0-exo-5,S-dimethanonaphthalene (dieldrin);

1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-

octahydro-l,4-end0-endo-5,6-dimethanonaphthalene (endrin); v

1 (or 3a), 4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- 4,7-methanoindene;

l, 1, l-trichloro-2,2-bis (p-methoxyphenyl ethane (methoxychlor) 1,l-dichloro2,2-bis(p-chlorophenyl)ethane;

chlorinated camphene having a chlorine content of 2-nitro-1,l-bis (p-chlorophenyl)butane; I

S-methyl N- (methylcarbamoyl oxy] thioacetimidate (methomyl) S-methyl 1-(dimethylcarbamoyl)-N-[ (methylcarbamoyl) oxy] thioformimidate;

l-naphthyl-N-methylcarbamate (Sevin carbaryl);

methylcarbamic acid, ester with phenol, 4-(dimethylamino)-3,5-dimethyl;

methylcarbamic acid, ester with 1,3-dithiolan-2-one oxime;

0,0-diethy1 O-[2-isopropyl-4-methylpyrimid-6-yl] thiophosphate;

0,0-dimethyl 1-hydroxy-2,2,2,-trichloroethyl phosphonate (diazinon) 0,0-dimethyl S-(1,2-dicarbethoxyethyl)dithiophosphate (malathion);

0,0-dimethyl O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-diethyl O-p-nitrophenyl thiophosphate (parathion);

0,0-dimethyl O-(3-chloro-4-nitrophenyl) thiophosphate;

dl-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopenten-1- one chrysanthemumate;

0,0-dimethyl 0,0-(2,2-dichlorovinyl) phosphate (DDVP dichlorovos);

mixture containing 53.3% Bulan, 26.7% Prolan and 20.0% related compounds;

0,0-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate;

0,0-dimethyl S- (4-oxo-1,2,3-benzotriazine-3 (4H)- yl-methyl) phosphorodithioate Guthion azinphosmethyl) bis-(dimethylamino)phosphonous anhydride;

0,0-diethyl O-(2-keto-4-methyl-1-7a-pyranyl) thiophosphate; t

0,0-diethyl (S-ethylmercaptomethyl) dithiophosphate;

calcium arsenate; v

sodium aluminofluoride;

dibasic lead arsenate;

2-chloroethyl 1-methyl-2-(p-tert-butylphenoxy)ethyl sulfite;

azobenzene;

ethyl 2-hydroxy-2,2-bis(4-chlorophenyl)acetate;

0,0-diethyl O-[2-(ethylmercapto)ethyl] thiophosphate Systox demeton);

2,4-dinitro-6-sec-butylphenol;

toxaphene;

O-ethyl O-p-nitrophenyl benzenethiophosphonate EPN);

4-chloropheny1 4-chlorobenzenesulfonate;

p-chlorophenyl phenyl sulfone;

tetraethyl pyrophosphate (TEPP);

1,1-bis-(p-chlorophenyl) ethanol;

1,l-bis-(p-chlorophenyl)2,2,2-trichloroethano (Kelthane dicofol);

p-chlorophenyl p-chlorobenzyl sulfide;

bis-(p-chlorophenoxy)methane; V

3-(1-methyl-2-pyrrolidyl)pyridine; 4

mixed ester of pyrethrolone and cinerolone keto-alcohols and two chrysanthemum acids;

cube and derris, both whole root and powdered; ryanodine; mixture of alkaloids known as veratrine; 2-(o-hydroxyphenyl)-1-3-dithiolane methylcarbamate ester; 2-(o-hydroxyphenyl)-l,3-dioxolane methylcarbamate ester; dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one esterfied with a mixture of cis and trans dl-chrysanthemum monocarboxylic acids; butoxypolypropylene glycol; I ethyl 2-hydroxy-2-2-bis(4-chlorophenyl)acetate (chlorobenzilate) p-dichlorobenzene; 2-butoxy-2-thiocyanodiethyl ether; naphthalene; methyl O -carbamylthiolacetohydroxamate; 1, l-dichloro-2,2-bis (p-ethylphenyl) ethane; methyl O-(methylcarbamyl)thiolacetohydroxamate (methomyl); p-dimethylaminobenzenediazo sodium sulfonate; 2-heptadecylimidazoline acetate (glyodin); tetralkylthiuram disulfides such as tetramethylthiuram disulfide or tetraethyl thiuram disulfide; sulfur; metal salts of ethylenebisdithiocarbamic acid or propylene-bisdithiocarbamic acids, e.g. manganese, zinc, iron and sodium salts (maneb or zineb); pentachloronitrobenzene; 2-l-(l-methylheptyl)-4,6-dinitrophenyl crotonate and other nitrophenol derivatives; methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate (benomyl); methyl-2-benzimidazole carbamate; 2-carboxyamino-l-benzimidazole carboxylic acid,

dimethyl ester; n-dodecylguanidine acetate (dodine); N- (trichloromethylthio phthalimide; N-trichloromethylthiotetrahydrophthalimide (captan) cis-N- 1, l ,2,2-tetrachloroethyl thio] -4-cyclohexene1,2-

dicarboximide; 2,4-dichloro-6-(o-chloroaniline)-s-triazine (Dyrene); bis (4-chl0rophenyl)-3-pyridylmethanol; 3,3'-ethylenebis(tetrahydro-4-6-dimethyl-2H-1,3,5-

thiadiazine-Z-thione) Triphenyltin hydroxide; 1,4-dichloro-2,5-dimethoxybenzene; Triphenyltin acetate;

, metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids; 2,6-dichloro-4-nitroanaline; tetrachloronitroananisole; hexachlorobenzene; methyl carbamic acid, ester with 2-methyl-2-(methylthiol) propionaldehyde oxime (Temik); hexachlorophene; methylmercury nitrile; tetrachloroquinone; 2,3-dichloro-1,4-napthoquinone; N-trichloromethylthiophthalimide; cupric hydroxide; tribasic copper sulfate; fixed copper; l,Z-dibromo-Z-chloropropene; 1,2-dibromo-3-chloropropane; dichloropropane-dichloropropene mixture; ethylene dibromide; chloropicrin; sodium monomethyldithiocarbamate; tetrachloroisophthalonitrile; 2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxathiin-4,4-

dioxide; streptomycin or other antibiotics; 2-(2,4,5-trichlorophenoxy)propionic acid; p-chlorophenoxyacetic acid;

The agricultural chemicals listed above are merely exemplary of the compounds which can be mixed with the active compounds of this invention and are not intended to any way limit the invention.

The additional pesticides are employed in mixtures or combinations in amounts ranging from one-tenth to ten times that of the compound or compounds of this invention. The proper choice of amounts for the added pesticides is readily made by one skilled in the art of protecting plants from pest depredations.

' The following examples are given to further illustrate methodsof' application'and formulations of this invention. Percentages are by weight.

EXAMPLE A Wettable Powder Percent 2 hydroxyimino 2 octylsulfonyl-N,N-diethylacetamide 50 Dioctyl sodium sulfosuccinate 1.5 Sodium ligninsulfonate 3 Low viscosity methyl cellulose 1.5 Attapulgite 44 The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. N0. 50 sieve (0.3 mm. opening) before packaging.

All compounds of the invention may be formulated in the same manner.

The above composition is suspended in water at 400 p.p.m., 80 ppm. and 16 ppm. of the active ingredient. Three potted tomato plants are sprayed to run-off with each of these suspension. Additional plants are sprayed with plain water to serve as checks. After the spray deposit has dried, the plants are uniformly inoculated with a zoospore suspension of the fungus Phytophthora infestans, the incitant of tomato late blight disease. The plants are placed under saturated moisture conditions in a humidity chamber for 24 hours, and further incubated for 3 days on a greenhouse bench.

Disease readings are taken at the time when the plants treated with water are completely defoliated by the late blight disease. Plants treated with the 16 ppm. concentration are about 50% defoliated. Plants treated with the 80 p.p.m. concentration have only a few lesions and are rated as about 15% defoliated. Tomatoes treated with the 400 ppm. concentration are essentially disease free and only an occasional lesion may be found.

EXAMPLE B Wettable Powder Percent Methylcarbamate of 2-hydroxyimino-2-methylsulfonyl- N,N-hexamethyleneacetamide 80 Sodium alkylnaphthalenesulfonate 2 Sodium lignin sulfonate 2 Synthetic amorphous silica 3 Kaolinite 13 The ingredients are thoroughly blended, passed through a hammer mill to produce an average particle size under 40 microns, re'blended and sifted through a US. No. 50 sieve (0.3 mm. openings) before packaging. 2,2-(l,10- decamethylenedisulfonyl) bis(2 hydroxyimino-N,'-N-diethylacetamide) is also formulated by the above procedure.

The above composition may be used in a manner similar to Example A with similar results.

EXAMPIJE C Wettable Powder Percent Mono-(2-chloroethyl) carbonate of 2-hydroxyimino-2- methylsulfonyl-N,N-dimethylacetamide 65 Dodecylphenol polyethylene glycol ether 2 Sodium ligninsnlfonate 4 Sodium silicoaluminate 6 Montmorillonite (calcined) 23' EXAMPLE D High Strength Concentrate and Dust Percent Methylcarbamate of 2 hydroxyimino-2-cyc1ohexylsulfonyl N,N-dimethylacetamide 98.5 Silica aerogel 0.5 Synthetic amorphous fine silica 1.0

The ingredients are blended and ground in a hammer mill to produce a high strength concentrate essentially all passing U.'S.S. No. 50 mesh. This material may then be shipped or formulated in a number of ways. For example, the following 25% dust can be prepared.

Percent High strength concentrate 25.4 Pyrophyllite 74.6

The materials are thoroughly blended and packaged for use.

The above 25 dust is applied to potted tomato plants by blowing a measured quantity into a chamber containing the plants. The quantity used is equal to 2.5 kilograms of the active ingredient per hectare. Additional plants are dusted with pyrophyllite alone to serve as checks. These tomato plants are uniformly sprayed with a zoo spore suspension of the fungus Phytophthora infestans, and placed in a saturated humidity chamber for 24 hours. After 3 additional days of incubation on a greenhouse bench the checks are completely defoliated by the late blight disease. Plants dusted with the composition of this invention remain disease free.

EXAMPLE E Dust Percent Methoxyacetate of 2-hydroxyimino-Z-methyl-sulfonyl- N,N-dimethylacetamide 1O Attapulgite 10 Talc' The active ingredient is blended with attapulgite and then passed through a hammer mill to produce particles of active substantially all below 200 microns. The ground concentrate is then blended with powdered talc until homogeneous.

I The above composition may be used in a manner similar to Example D with similar results.

EXAMPLE F Water Soluble Powder Percent 2-hydroxyimino 2 methylsulfonyl-N,N-dimethylacetamide 95.0 Dioctyl sodium sulfosuccinate 0.5 Calcium ligninsulfonate 1.0 Silicaaerogel 3.5

The ingredients are blended and coarsely ground in a hammer mill so that only a few percent of the active exceeds 250 microns in size. When added to water with stirring, the coarse powder initially disperses and then the active ingredient dissolves so that no further stirring is needed during application.

The above composition is dissolved in water at 80 p.p.m., 16 p.p.m. and 3.2 p.p.m. of the active ingredient. Four potted apple seedlings selected to have at least two disease-susceptible leaves at the growing point, are sprayed to runoff with each of these suspensions. Four additional seedlings are sprayed with water to serve as checks. After the spray deposit has dried, the susceptible growing tips are inoculated with a conidial suspension of the fungus Venturia inaequalis, commonly, apple scab. This inoculation is effected by use of a hand-operated atomizer from above at p.s.i. Still wet, the seedlings are placed in a humidity chamber at 20 C. and 100% relative humidity for 48 hours after which they are removed to a greenhouse bench for further incubation. Disease ratings are made after thirteen days. At this reading the inoculated leaves of the checks are covered with a velvety coating of sporulating fungus. The seedlings treated with the 3.2 p.p.m. concentration have about disease coverage; those treated with the 16 p.p.m. treatment have only a few lesions comprising less than 10% of the leaf surfaces. The 80 p.p.m. concentration completely controls apple scab.

EXAMPLE G Aqueous Suspension Percent p-Bromocarbanilate of 2-hydroXyimino-2-methylsulfonyl-N,N-dimethylacetamide 25 Hydrated attapulgite 3 Crude calcium/magnesium lignin sulfonate 10 Sodium dihydrogen phosphate 0.5 Water 61.5

. The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 5 microns.

The above composition may be used in a manner similar to Example F with similar results.

EXAMPLE H Emulsifiable Concentrate Percent Chloroacetate of 2-hydroxyimino-2-methylsulfonyl- N,N-dimethylacetamide 32.5 Chlorobenzene 61. Sorbitan monostearate and polyoxyethylene condensates thereof 6.0

The above composition may be used in a manner similar to Example F with similar results.

Any of the chlorobenzene-soluble compounds of this invention may be formulated in a similar manner and when applied as in Example F, give similar results.

EXAMPLE I Emulsifiable Concentrate Percent 2 hydroxyimino 2 octylsulfonyl-N,N-diethylacetamide 25 Xylene 72 Blend of oil soluble sulfonates and polyoxyethylene ethers The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in the packaging line to insure the absence of any undissolved matter in the final product.

The above composition is diluted in water at 400 p.p.m. of the active ingredient. Three potted tomato plants, 8"- 9" tall, are sprayed to run-off with the suspension. Three additional tomato plants are sprayed with water to serve as untreated controls. The spray deposit is allowed to dry overnight on the plants after which one inch of rainfall is simulated on a turntable using two spray nozzles from above and one from below. After drying, again overnight, the plants are uniformly inoculated with a zoospore suspension of the fungus Phytophthora infestans, the incitant of tomato late blight disease. Still wet with inoculum, the plants are placed in a humidity chamber at 20 C. and relative humidity for approximately 20 hours then further incubated for 3 days on a greenhouse bench. Disease ratings are made at this time. I

The untreated controls are completely defoliated by the late blight disease. The treated plants, on the other hand, are essentially disease free.

Any of the xylene-soluble compounds of this invention, such as 2,2'-(1,8-octamethylenedisulfonyl)bis(2-hydroxyimino-N,N-dipropylacetamide), can be formulated in a similar manner and when applied, give similar results.

EXAMPLE I Solution Percent 2 hydroxyimino 2 octylsulfonyl-N,N-diethylacetamide 35 Dimethylformamide 65 The ingredients are combined and stirred to produce a solution suitable for direct application.

What is claimed is: 1. A compound of the formula:

NC(IJ=NOR S (0),,

wherein n is 1 or 2;

R is alkyl of 1 through 12 carbon atoms; alkyl of 3 through 12 carbon atoms substituted with 1 chlorine atom; alkenyl of 3 through 4 carbon atoms; cyclm alkyl of 3 through 8 carbon atoms; cycloalkylalkyl of 6 through 7 carbon atoms; phenyl; benzyl; or

wherein R R and R are as defined below, p is 1 or 2, and R is phenylene, xylylene, or alkylene of 2 through 18 carbon atoms;

R and R are each separately selected from the group consisting of alkyl of 1 through 12 carbon atoms; alkenyl of 3 through 4 carbon atoms; cycloalkyl of 3 through 10 carbon atoms; cycloalkenyl of 5 through 8 carbon atoms; cycloalkylalkyl of 6 through 7 carbon atoms; or benzyl; with the provisos that (1) only one of R and R can be benzyl, and (2) the sum of carbon atoms in R and R can total no more than 12, except where both R and R are alkyl;

R is hydrogen;

wherein R is alkyl of 1 through 8 carbon atoms; propargyl; alkenyl of 3 through 4 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; benzyl; phenyl; or phenyl substituted with 1 or 2-substituents selected from halogen, nitro, methoxy, and methyl.

2. Compound of Claim 1 having the formula wherein R and R are each separately selected from the group consisting of alkyl of 1 through 6 carbon atoms; and R is phenylene; xylylene; or alkylene of 2 through 12 carbon atoms.

3. Compound of Claim 2: 2,2'-(1,4-tetramethylenedisulfonyl) bis(2-hydroxyimino-N,N-diethylacetamide 4. A compound of Claim 1 wherein R is hydrogen.

5. A compound of Claim 1 wherein R is R R 0 =(3- N 6. A compound of Claim wherein R is hydrogen.

7. The compound of Claim 1 in which R R and R are each methyl.

8. The compound of Claim 1 in which R is cyclohexyl, R and R are each methyl, and R is H.

9. The compound of Claim 1 in which R is octyl, R and R are each ethyl, and R is H.

10. The compound of Claim 1 in which R is hexy R and R are each ethyl, and R is H.

11. Compound of Claim 1 in which R is dodecyl, R and R are each ethyl, and R is H.

34 12. Compound of Claim 1 in which R is methyl, R and R are each ethyl, and R is H.

References Cited OTHER REFERENCES Metcalf et al.: Metabolism of 2-Methyl, Etc., 1966), J. Ag. & Food Chem., 14, pp. 579-84 (1966).

GLENNON H. HOLLRAH, Primary Examiner US. Cl. X.R.

260239 A, 239 B, 247.1, 293.62, 293.85, 326.82, 453 R, 558 S, 562 S, 562 N; 424244, 248, 267, 274, 320, 324

gg g v UNITED STATES PATENT OFFICE CERTEFICATE OF CORRECTION June 25, 197 1 Patent No. 3, 19,7 Dated Inventor(s) It is certified that error appears in the above-identified patent and that said- Letters Patent are hereby corrected as shown below:

In Column 1,, line 5 after "19703" insert as'signor to E. I. du Pont de- Nemours and Company, Wilmington, Delaware--.

Signed and sealed this 29th day of October 1974.

'(SEAL) I Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN I Commissioner of Patents Attesting Officer